CN103328212B - Layered polyester film and hardcoat film - Google Patents

Abstract

[Problem] To provide: a layered polyester film which shows highly long-lasting adhesion of various kinds to hardcoat layers having various functions represented by a UV-absorbing function, etc. and which shows satisfactory appearance properties due to diminished interference unevenness; and a hardcoat film. [Solution] A layered polyester film which comprises a substrate polyester film (layer S) and, formed on at least one surface thereof, a covering film (layer C) comprising a polyester resin as a major component, the layered polyester film being characterized in that the surface of the covering film (layer C) has a wetting tension of 35-45 mN/m and the polyester resin contained in the covering film (layer C) satisfies the following (a) to (c). (a) The covering film (layer C) contains a group of polyesters (A) having a glass transition temperature (Tg) of 110-140 C and a group of polyesters (B) having a glass transition temperature (Tg) of 40-90 C. (b) At least the group of polyesters (A) or the group of polyesters (B) contains both a monomer having a sulfonic acid component and a monomer having a polycarboxylic acid component having a basicity of 3 or higher. (c) The proportion of the group of polyesters (A) to the group of polyesters (B) is from 10/90 to 60/40.

Description

Laminated polyester film and hard coat film

Technical field

The present invention relates to the laminated polyester film of cohesive excellence, particularly relate to as touch-screen, shaping to band etc. in the base material of hard conating film that uses use time, with initial bond power and the resistance to wet adhesion excellence of hard conating, and then there is the laminated polyester film and hard coat film of interfering uneven also repressed good appearance.Say in further detail, relating to the hard conating for imparting UV absorption function and/or the such various functions of anti-pollution function, also there is broad range and the laminated polyester film of good bonding force and hard coat film.

Background technology

Polyester film due to the mechanical property, electrical property, dimensional stability, heat resistance, the transparency, chemical resistance etc. of its excellence for various industrial materials purposes, packaging material purposes, magnetic material applications etc.Particularly in order to augment the case hardness of polyester film and/or resistance to nuzzling up property and arrange hard conating on surface, improve the hard coat film of marresistance and/or abrasion performance; due to as the surface protection film of the liquid crystal display of their main application and/or the such flat-panel monitor of plasma display and/or reflectance coating, touch-screen, display board, label, window pastes, surface adds decoration materials etc. expansion; in recent years more and more become to grow up to large market, estimate also there is large growth in the future.

These polyester films with hard conating are by obtaining at substrate polyester film superimposed layer hard conating.But, when substrate polyester film directly arranges hard conating, poor adhesion and/or due to by hard conating and the intermembranous refringence of substrate polyester and the interference of the light produced is uneven and deteriorated appearance that is that cause becomes problem, in order to improve these problems, studying the stack membrane that specific formation is set on substrate polyester film.(patent document 1,2)

But, in recent years, when hard coat film especially for portable equipment, in order to prevent by the deterioration of UV-induced tone, make in hard conating containing ultra-violet absorber (patent document 3,4), give the anti-pollution function (patent document 5) for preventing dirt from adhering to, and/or give mouldability (patent document 6) etc. in order to the shape chased after from component, thus the more and more progress of the functionalization of hard conating, be applicable to each purposes and carried out diversified design.The result of the variation progress of such hard conating is, for the stack membrane on substrate polyester film, require to there is broad range and good bonding force to the hard conating of all designs, but the narrow scope of bonding force under the prior art, thus needs the design of applicable hard conating and stack membrane is carried out upgrading.Therefore, sometimes productivity ratio and/or cost poor, according to circumstances need in addition to tackle and lose the function etc. of hard conating.Particularly when requiring the purposes of Ultraviolet Light, need in thin hard conating, add a large amount of UV absorbents, therefore fusible reduction is remarkable, can not obtain the problem of sufficient performance in addition.And then, except the raising of common initial bond power, even if also do not lose the height durability of bonding force under also needing high temperature, high humidity, require the polyester film with the excellent adhesion taking into account them.

Prior art document

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2007-253512 publication

Patent document 2: International Publication No. 2009/145075 pamphlet

Patent document 3: Japanese Unexamined Patent Publication 2005-335163 publication

Patent document 4: Japanese Unexamined Patent Publication 2010-83029 publication

Patent document 5: Japanese Unexamined Patent Publication 2010-152331 publication

Patent document 6: Japanese Unexamined Patent Publication 2009-220280 publication

Summary of the invention

The problem that invention will solve

The object of the invention is, in view of the problem of above-mentioned prior art, provide: to show extensively with the hard conating that is various function of representative such as UV absorption function and the bonding force of excellent in te pins of durability and then show the laminated polyester film and hard coat film of interfering uneven also repressed good appearance characteristic with having.

For solving the method for problem

The present invention, in order to solve above-mentioned problem, makes with the following method.

(1). a kind of laminated polyester film, it is characterized in that, be the laminated polyester film of the stack membrane (C layer) of principal component with mylar at least one lamination of substrate polyester film (S layer), the wetting tension on stack membrane (C layer) surface is 35 ~ 45mN/m, and mylar contained in stack membrane (C layer) meets following (a) ~ (c):

A () is polyester (A) group of 110 ~ 140 DEG C and glass transition temperature (Tg) containing glass transition temperature (Tg) in stack membrane (C layer) is polyester (B) group of 40 ~ 90 DEG C,

(b) at least organize in polyester (A) group and polyester (B) any one in, containing the monomer with sulfonic acid composition and the monomer of polybasic carboxylic acid composition with more than 3 yuan,

C blending ratio that () polyester (A) group and polyester (B) are organized is 10/90 ~ 60/40.

(2). a kind of laminated polyester film, it is characterized in that, be the laminated polyester film of the stack membrane (C layer) of principal component with mylar at least one lamination of substrate polyester film (S layer), form in the mylar of this stack membrane (C layer) containing the monomer with sulfonic acid composition, and the wetting tension on stack membrane (C layer) surface is 35 ~ 45mN/m, for analyzing the surperficial following 2 secondary ion peak kinds obtained of stack membrane (C layer) with time-of-flight type 2 secondary ion mass spectrum (TOF-SIMS), the standardized value of intensity is in following ranges

CHO ₂ ^-be 0.3 × 10 ^-2~ 1.5 × 10 ^-2,

SO ₃ ^-be 0.2 × 10 ^-2~ 2.0 × 10 ^-2.

(3). the laminated polyester film according to (1) or (2), mylar contained in stack membrane (C layer), be polyester (A) group of 110 ~ 140 DEG C and glass transition temperature (Tg) containing glass transition temperature (Tg) be polyester (B) group of 40 ~ 90 DEG C, and polyester (A) group and polyester (B) group are containing the monomer with sulfonic acid composition and the monomer of polybasic carboxylic acid composition with more than 3 yuan, and then, whole monomer components 100 molar part contained in relative to polyester (A) group, the containing ratio with the monomer of sulfonic acid composition in this monomer component is SA (molar part), the containing ratio with the monomer of the polybasic carboxylic acid composition of more than 3 yuan is CA (molar part), and relative to whole monomer components 100 molar part contained in polyester (B) group, the containing ratio with the monomer of sulfonic acid composition in this monomer component is SB (molar part), when the containing ratio with the monomer of the polybasic carboxylic acid composition of more than 3 yuan is CB (molar part), meet with following formula (d) ~ (g),

1≤SA≤10 ... formula (d)

1≤SB≤10 ... formula (e)

1≤CA≤10 ... formula (f)

1≤CB≤10 ... formula (g).

(4). the laminated polyester film according to any one of (1) ~ (3), in stack membrane (C layer) containing melamine series and/or azoles quinoline system crosslinking agent, the content of this crosslinking agent is relative to mylar content 100 weight portion, containing 20 ~ 80 weight portions.

(5). the laminated polyester film according to any one of (1) ~ (4), containing acrylic resin in stack membrane (C layer), the content of this acrylic resin is relative to mylar content 100 weight portion, containing 5 ~ 30 weight portions.

(6). the laminated polyester film according to any one of (1) ~ (5), the spectral reflectance curve of stack membrane (C layer) side surface exists at wavelength 500 ~ 600nm becomes minimum wavelength X min, is 4.0 ~ 6.0% at the reflectivity Rmin of λ min.

(7). a kind of hard coat film, it is stack membrane (C layer) the superimposed layer hard conating of laminated polyester film described in any one in (1) ~ (6).

(8). a kind of manufacture method of laminated polyester film, it has following operation: mylar melting is shaped to the operation of sheet, carries out biaxial stretch-formed operation at length direction and width and at least in the side face side of film, stack membrane is carried out the operation of lamination, and this operation of stack membrane being carried out lamination comprises by being coated with at least side of substrate polyester film (S layer) operation that following resin combination carrys out laminated resin layer

Described resin combination is be at least polyester (A) group of 110 ~ 140 DEG C and glass transition temperature (Tg) containing glass transition temperature (Tg) is the resin combination that the polyester (B) of 40 ~ 90 DEG C is organized, polyester (A) group and polyester (B) organize at least in any one, containing having the monomer of sulfonic acid composition and having the monomer of polybasic carboxylic acid composition of more than 3 yuan, and the weight rate that polyester (A) group and polyester (B) are organized is 10/90 ~ 60/40.

(9). the manufacture method of the laminated polyester film according to (8), described resin combination meets following necessary condition:

Whole monomer component 100mol% contained in relative to polyester (A), the containing ratio with sulfonic monomer in this monomer component is SA (mol%), the containing ratio with the monomer of the polybasic carboxylic acid base of more than 3 yuan is CA (mol%), and relative to whole monomer component 100mol% contained in polyester (B), the containing ratio with sulfonic monomer in this monomer component is SB (mol%), when the containing ratio with the monomer of the polybasic carboxylic acid base of more than 3 yuan is CB (mol%), meet with following formula (d) ~ (g)

1≤SA≤10 ... formula (d)

1≤SB≤10 ... formula (e)

1≤CA≤10 ... formula (f)

1≤CB≤10 ... formula (g).

(10). the manufacture method of the laminated polyester film according to (8) or (9), described resin combination meets following necessary condition:

Resin combination further containing melamine series and/or azoles quinoline based compound, the content of this compound, relative to mylar content 100 % by weight, is 20 % by weight ~ 80 % by weight.

(11). the manufacture method of the laminated polyester film according to any one of (8) ~ (10), described resin combination meets following necessary condition:

Resin combination is further containing acrylic resin, and the content of this acrylic resin, relative to mylar content 100 % by weight, is 5 % by weight ~ 30 % by weight.

The effect of invention

According to the present invention; can be provided as when the surface protection film of liquid crystal display and/or the such flat-panel monitor of plasma display and/or reflectance coating, touch-screen, display board, label, the base material of hard conating films that uses during window pastes, surface adds decoration materials etc. use; show extensively and the bonding force of excellent in te pins of durability with the hard conating of various design, and then the laminated polyester film of interfering uneven also repressed good appearance characteristic can be obtained.

Accompanying drawing explanation

Fig. 1 is the schematic diagram of DSC curve.

Fig. 2 is an example of the reflectance map of stack membrane (C layer) side of laminated polyester film.

Detailed description of the invention

Laminated polyester film of the present invention, must have stack membrane (C layer) at least side lamination of substrate polyester film (S layer).When there is no stack membrane (C layer), not enough with the cohesive of the functional layer such as the hard conating be stacked on film.

The present invention relates to and have extensively and the laminated polyester film of the bonding force of excellent in te pins of durability with the hard conating of various design, as its index, on stack membrane (C layer) surface, stack membrane (C layer) is 3 ~ 5 with the wet-heat resisting bondability index of the hard conating containing ultra-violet absorber.By making the principal component of formation stack membrane (C layer) be mylar, can show with the good adhesion of hard conating and lamination hard conating after interfere uneven repressed good appearance.Stack membrane (C layer) must show the bonding force with the endurance excellence of the hard conating of broad variety in addition, sometimes with the critical appraisal such with the wet-heat resisting adhesion test of the hard conating containing ultra-violet absorber of the most difficult performance bonding force, the bonding force that performance is good is also required.When wet-heat resisting bondability index is less than 3, become insufficient with the bonding force of hard conating.In addition, for the evaluation method of the wet-heat resisting bondability index with the hard conating containing ultra-violet absorber, in embodiment, 4 (A) of [determination method of physical property] are middle records.In addition, about the method making wet-heat resisting bondability index in above-mentioned scope, such as, can realize for formation described later preferably by making stack membrane (C layer).

Form in the mylar of stack membrane of the present invention (C layer), must containing the monomer with sulfonic acid composition (sulfonic group and/or its salt).In order to improve the bonding force with hard conating, and then in order to arrange thin stack membrane equably when stack membrane (C layer) is formed, mylar must demonstrate water-soluble or good water dispersible, therefore must containing the monomer with sulfonic acid composition in polyester resin layer.By containing sulfonic acid composition in mylar, the hydrophily of resin increases, thus obtains extra high effect in raising with the initial bond power of hard conating.The wetting tension on stack membrane of the present invention (C layer) surface is 35 ~ 45mN/m, is preferably 36 ~ 43mN/m.When wetting tension is more than 45mN/m, due to form stack membrane (C layer) polyester resin component in hydrophilic radical too much, and be easily subject to by the impact of humidity, sometimes the durability of bonding force and wet-heat resisting poor adhesion.When contrary wetting tension is less than 35mN/m, because hydrophilic radical is very few, thus bonding force itself reduces and/or can not obtain uniform stack membrane (C layer) sometimes.The method making wetting tension in above-mentioned scope is not particularly limited, such as, can realizes preferably by the content of the polybasic carboxylic acid composition adjusting sulfonic acid composition contained in stack membrane (C layer) and/or more than 3 yuan described later.

In the present invention, in order to take into account with the uniformity of the bonding force of hard conating and stack membrane (C layer) and preferably in stack membrane (C layer) containing the polybasic carboxylic acid composition of more than 3 yuan.Think by making the mylar of formation stack membrane (C layer) contain sulfonic acid composition, in raising with the bonding force at the initial stage of hard conating, there is special result as mentioned above, but find tendency slightly poor in the durability (wet-heat resisting cohesive) of bonding force.On the other hand, carboxylic acid composition is compared with sulfonic acid composition, to the little but bonding force excellent in te pins of durability of contribution that initial bond power improves, also comprise in addition in order to ensure the uniformity of stack membrane (C layer) and give hydrophilic effect to resin, in order to take into account and the initial bond of hard conating and wet-heat resisting cohesive, and obtain uniform stack membrane, preferably except having the monomer component of sulfonic acid composition, also together containing the monomer of polybasic carboxylic acid composition with more than 3 yuan.In addition, in the present invention, the monomer with sulfonic acid composition that contains and have the monomer of carboxylic acid composition of more than 3 yuan in the mylar forming stack membrane (C layer), can be in mylar of more than two kinds and contain.Element contained in stack membrane (C layer) and combining information thereof, by using x-ray photoelectron optical spectroscopy (ESCA) or time-of-flight type 2 secondary ion mass spectrum (TOF-SIMS) direct-detection, can carry out quantitative analysis for the sulfonic acid composition contained, carboxylic acid composition by its result.Such as, in time-of-flight type 2 secondary ion mass spectrum (TOF-SIMS), by the CHO deriving from carboxylic acid group measured with the method described in " determination method of physical property " in embodiment 7 ₂ ^-and derive from sulfonic group SO (m/z:45.00) ₃ ^-(m/z:79.96) 2 secondary ion peak intensities analyze carboxylic acid group in stack membrane (C layer) and sulfonic acid base unit weight.In addition, as respective standard value, CHO ₂ ^-be preferably 0.30 × 10 ^-2~ 1.50 × 10 ^-2, be more preferably 0.40 × 10 ^-2~ 1.00 × 10 ^-2, SO ₃ ^-be preferably 0.20 × 10 ^-2~ 2.00 × 10 ^-2, be more preferably 0.50 × 10 ^-2~ 1.50 × 10 ^-2.Initial bond and wet-heat resisting cohesive can be taken into account, thus preferably when meeting above-mentioned scope.

In the present invention, be polyester (A) group of 110 DEG C ~ 140 DEG C and glass transition temperature containing glass transition temperature (Tg) in stack membrane (C layer) be polyester (B) group of 40 DEG C ~ 90 DEG C, the ratio that polyester (A) group and polyester (B) are organized is preferably 10/90 ~ 60/40.The glass transition temperature (Tg) that polyester (A) is organized is higher, consider by containing polyester (A) group, even if the variation of molecular structure also tails off under the environment under high temperature and/or high humidity, and the durability of bonding force and wet-heat resisting cohesive improve.When not organizing containing polyester (A) and/or when ratio is less than 10/90, wet-heat resisting cohesive (adhesion durability) is poor sometimes.In addition, the motility that polyester (B) group has lower glass transition temperature (Tg) thus molecule is high, consider, by containing polyester (B) group, show the bonding force widely not relying on hard conating kind, and/or initial bond power to improve.When not organizing containing polyester (B) or when the ratio organized of polyester (B) is less than 60/40, initial bond is poor sometimes.In addition, meet polyester (A) group, mylar that polyester (B) is organized can be single, also can be the mixture of multiple mylar, preferably meet the weight rate of the resin of each polyester group in above-mentioned scope.

The glass transition temperature (Tg) that polyester of the present invention (A) is organized is 110 ~ 140 DEG C, is preferably 120 ~ 140 DEG C.When glass transition temperature (Tg) is less than 110 DEG C, poor with the wet-heat resisting cohesive (adhesion durability) of hard conating, when glass transition temperature (Tg) is more than 140 DEG C, poor and/or resin itself changes too upright and outspoken with the initial bond power of hard conating, thus finds that water dispersible is poor, the tendency of the deteriorated appearance of stack membrane (C layer).In addition, the glass transition temperature (Tg) that polyester of the present invention (B) is organized is 40 ~ 90 DEG C, is preferably 50 ~ 85 DEG C.When glass transition temperature (Tg) is less than 40 DEG C, sometimes poor with the wet-heat resisting cohesive (adhesion durability) of hard conating, when glass transition temperature (Tg) is more than 90 DEG C, sometimes poor with the initial bond power of hard conating.The glass transition temperature (Tg) of mylar adjusts by the combination of the monomer component of the formation mylar of explained later and/or its molecular weight.Specifically, by containing the upright and outspoken compositions such as benzene skeleton, naphthalene skeleton, fluorene skeleton in the polyester, glass transition temperature (Tg) can be improved, by the composition containing the long fatty family of point subchain such as aklylene glycol and/or such as neopentyl glycol, glass transition temperature (Tg) can be reduced.In order to obtain the higher resin of glass transition temperature (Tg) as organized in polyester (A), preferably in molecule, contain upright and outspoken composition, be in particular the monomer component with naphthalene skeleton and/or fluorene skeleton, preferably make its content be that 30 ~ 80 molar part are prepared relative to the monomer component of mylar entirety.In addition, for polyester (B) group, preferably containing the monomer component in molecule with phenyl ring, the preferred contraposition at phenyl ring has the functional group's (being specially carboxyl and/or hydroxyl) contributing to ester bond further.These content with the monomer of phenyl ring are preferably made to contain 30 ~ 50 molar part to be prepared relative to the monomer component of mylar entirety.

Meet the mylar that the polyester (A) in the present invention is organized, preferably contain in its constituent: the monomer of the monomer containing sulfonic acid composition and the polybasic carboxylic acid composition containing more than 3 yuan.And then, when whole monomer components of the mylar that formation polyester (A) is organized are 100 molar part, the containing ratio (SA (molar part)) preferably with the monomer of sulfonic acid composition is 1 ~ 10 molar part, more preferably 3 ~ 5 molar part.In addition, the containing ratio (CA (molar part)) preferably containing the monomer of the polybasic carboxylic acid composition of more than 3 yuan is 1 ~ 10 molar part, more preferably 3 ~ 8 molar part.Similarly, form mylar (B) mylar organized, preferably preferably contain in its constituent: the monomer of the monomer with sulfonic acid composition and the polybasic carboxylic acid composition with more than 3 yuan.And then, when whole monomer components of the mylar that formation polyester (B) is organized are 100 molar part, the containing ratio (SB (molar part)) with the monomer of sulfonic acid composition is preferably 1 ~ 10 molar part, more preferably 3 ~ 5 molar part.In addition, the containing ratio (CB (molar part)) of the monomer containing the polybasic carboxylic acid compositions of more than 3 yuan is preferably 1 ~ 10 molar part, more preferably 3 ~ 8 molar part.By organize at different 2 kinds of polyester (A) groups, the polyester (B) of glass transition temperature forming stack membrane (C layer) at least in arbitrary group, containing there is the monomer of sulfonic acid composition and there is the monomer component of polybasic carboxylic acid composition of more than 3 yuan, and make respective amount in above-mentioned scope, thus can obtain, with the laminated polyester film of the balancing good of the initial bond power of the broad range of hard conating and wet-heat resisting cohesive (adhesion durability), being preferably bonded as 3 ~ 5 with the moisture-proof of the hard conating containing ultra-violet absorber.In addition, and then by different 2 kinds of polyester (A) groups of glass transition temperature, polyester (B) both groups, the monomer component of the monomer making to have sulfonic acid composition and the polybasic carboxylic acid composition with more than 3 yuan, in above-mentioned scope, can obtain the laminated polyester film with the balance of the initial bond power of the broad range of hard conating and wet-heat resisting cohesive (adhesion durability) especially excellence.Special in polyester (B) group, by containing the monomer with sulfonic acid composition, broad range can be showed and good initial bond, if but sulfonic acid composition is too much, then wet-heat resisting cohesive (adhesion durability) reduces, therefore preferably containing the carboxylic acid composition that wet-heat resisting cohesive (adhesion durability) is excellent, and be suitable content.In addition, in polyester (A) group, by containing carboxylic acid composition, wet-heat resisting cohesive (adhesion durability) can be showed, but only carboxylic acid composition can not give full play to its wet-heat resisting cohesive (adhesion durability) sometimes.Presumption this is because, in the adhesion stage at the initial stage with hard conating, the sulfonic acid composition contained by polyester (A) group plays a role, thus contributes to being showed the high bonding of durability by carboxylic acid composition.In addition, the water-soluble or water dispersible of the resin that the polyester (A) that only during carboxylic acid composition, glass transition temperature (Tg) is higher is organized becomes insufficient sometimes, the sulfonic acid composition preferably containing appropriateness.In addition, in the present invention, the monomer with sulfonic acid composition contained in polyester (A) group and/or polyester (B) group and there is the monomer of carboxylic acid composition of more than 3 yuan, can be in the mylar of more than two kinds belonging to each polyester group and contain, the total content in preferred each mylar group is in above-mentioned scope.

Stack membrane of the present invention (C layer), the reverberation being preferably designed to the interface between hard conating and laminated polyester film of the present invention is minimum in visible region.The uneven reverberation due to air/hard conating interface of interference of hard coat film and the reflecting interference at hard conating/rete interface occur, and therefore by making the reverberation at hard conating/rete interface minimum, interference can be suppressed uneven.In order to have above-mentioned such characteristic, the spectral reflectance of the preferred stack membrane of laminated polyester film of the present invention (C layer) side becomes minimum wavelength X min and is present between wavelength 500 ~ 600nm, more preferably 530nm ~ 570nm.Wavelength X min, when the scope of 500 ~ 600nm as center, visible region, not easily finds to interfere uneven and good, above-mentioned scope outward time, sometimes interfere uneven deterioration, thus not preferred.In addition, the reverberation considering the reverberation at interface between air layer/stack membrane (C layer) and stack membrane (C layer)/substrate polyester film (S layer) interface inversion phase and cancelling each other out each other, thus reflectivity becomes minimum wavelength X min and adjusts the composition of stack membrane (C layer) by the mode that the difference (refractive index of the thickness × 2 × easy adhesive layer of easy adhesive layer) of the optical path length advanced with both light is 1/2 of wavelength 500 ~ 600nm and thickness realizes.Describe after being formed in about stack membrane concrete.

In addition, in the present invention, the reflectivity Rmin that the spectral reflectance of preferred stack membrane (C layer) side becomes minimizing wavelength X min is 4.0% ~ 6.0%, more preferably 4.8% ~ 5.3%.Rmin, when above-mentioned scope is outer, interferes uneven deterioration sometimes.With stack membrane (C layer) the substrate polyester film (S layer) that adjoins and the refringence that is stacked on the hard conating on stack membrane (C layer) little, can reduce between hard conating/stack membrane (C layer) and the reflectivity at interface between stack membrane (C layer)/substrate polyester film (S layer), thus preferred, both reflectivity are near then by interfering the reduction effect of the reverberation caused large in addition, thus preferably.The refractive index of common hard conating is 1.45 ~ 1.55, the refractive index of substrate polyester film (S layer) is 1.60 ~ 1.70, the state that the uneven maintenance of interference above-mentioned within the scope of this is good, therefore the reflectivity Rmin of stack membrane (C layer) side of laminated polyester film must in above-mentioned scope.This is realized by the refractive index of adjustment stack membrane (C layer), describes for after being specifically formed in of stack membrane.

Mylar contained in stack membrane of the present invention (C layer), refers to that main chain or side chain have the mylar of ester bond, the I by following) or method II) obtain.In addition, also can use and use I) and method II) (using dicarboxylic acid component, diol component and there is functional group's (hydroxyl) of alcoholic of more than 1 and the carboxyl of more than 1 composition as constituent, make them carry out the method for polycondensation reaction).

I) using dicarboxylic acid component and diol component as constituent, make both carry out the method for polycondensation reaction.

II) using the composition of functional group's (hydroxyl) of alcoholic and the carboxyl of more than 1 with more than 1 as constituent, carry out the method for polycondensation reaction.

For the monomer component forming mylar contained in stack membrane of the present invention (C layer), be not particularly limited, but the aromatic series as illustrated in following, aliphatic, alicyclic dicarboxylic acids and/or diol component can be used.As above-mentioned dicarboxylic acid component, terephthalic acid (TPA), M-phthalic acid, phthalic acid, phthalic acid, 2,5-dimethyl terephthalic acid, biphenyl dicarboxylic acid, 1,2-biphenoxyl ethane-p can be used, p '-dioctyl phthalate, phenyl indan dioctyl phthalate etc.In addition, as this aliphatic and alicyclic dicarboxylic acids, can enumerate and use butanedioic acid, adipic acid, decanedioic acid, dodecanedioic acid, dimeric dibasic acid, 1,3-pentamethylene dioctyl phthalate, 1,2-cyclohexane cyclohexanedimethanodibasic, 1,4-cyclohexane cyclohexanedimethanodibasic etc. and their ester formative derivative, but be not limited to this.In addition, as diol component, spent glycol can be made, diethylene glycol (DEG), polyethylene glycol, propane diols, polypropylene glycol, 1,3-PD, 1,3-BDO, BDO, 1,5-PD, 1,6-hexylene glycol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethyl hexane-1,3-glycol, neopentyl glycol, 2-ethyl-2-butyl-1,3-PD, 2-ethyl-2-isobutyl group-1,3-PD, 3-methyl isophthalic acid, 5-pentanediol, 2,2,4-trimethyl-1,6-hexylene glycol, 1,2-CHDM, 1,3-CHDM, 1,4-CHDM, TMCBD, 4,4 '-thiodiphenol, bisphenol-A, 4,4 '-methylene biphenol, 4,4 '-(dicyclo [2.2.1]-2-in heptan subunit) bis-phenol, 4,4 '-dihydroxybiphenyl, o-dihydroxy benzene, Meta-dihydroxybenzene, hydroquinol, 4,4 '-isopropylidene phenol, pentamethylene-1,2-glycol, cyclohexane-1,2-glycol, cyclohexane-Isosorbide-5-Nitrae-glycol etc., but be not limited to this.

In the present invention, in the mylar that formation polyester (A) is organized, preferably there is naphthalene skeleton and/or fluorene skeleton.By giving mylar with fluorene skeleton and/or naphthalene skeleton, polyester resin backbone becomes upright and outspoken, can improve the glass transition temperature (Tg) of mylar.In addition, the high index of refractionization of mylar also becomes possibility, can make the scope that the reflectivity Rmin on above-mentioned stack membrane (C layer) surface is being applicable to, thus preferably.At above-mentioned I) method in, by using, there is the dicarboxylic acid component of naphthalene skeleton and/or fluorene skeleton, or use the diol component with naphthalene skeleton and/or fluorene skeleton, the mylar with above-mentioned naphthalene skeleton and/or fluorene skeleton can be obtained.In addition, at above-mentioned II) method in, there is naphthalene skeleton and/or fluorene skeleton and the composition with functional group's (hydroxyl) of the alcoholic of more than 1 and the carboxyl of more than 1 by using, the mylar with above-mentioned naphthalene skeleton and/or fluorene skeleton can be obtained.

As the dicarboxylic acid component with naphthalene skeleton or fluorene skeleton, can enumerate such as, two (tert-Butoxycarbonyl-methyl) fluorenes of 9,9-, two [2-(tert-butoxycarbonyl) ethyl] fluorenes of 9,9-, two [1-(tert-butoxycarbonyl) ethyl] fluorenes of 9,9-, two [2-(the tert-butoxycarbonyl)-1-cyclohexyl-ethyl] fluorenes of 9,9-, two [2-(the tert-butoxycarbonyl)-1-phenylethyl] fluorenes of 9,9-, two [1-(tert-butoxycarbonyl) propyl group] fluorenes of 9,9-, two [2-(tert-butoxycarbonyl) propyl group] fluorenes of 9,9-, two [2-(the tert-butoxycarbonyl)-1-Methylethyl] fluorenes of 9,9-, two [2-(the tert-butoxycarbonyl)-1-methyl-propyl] fluorenes of 9,9-, two [2-(tert-butoxycarbonyl) butyl] fluorenes of 9,9-, two [2-(the tert-butoxycarbonyl)-1-methyl butyl] fluorenes of 9,9-, two [5-(tert-butoxycarbonyl) amyl group] fluorenes of 9,9-, Isosorbide-5-Nitrae-naphthalenedicarboxylic acid, NDA etc., but be not limited to this.In addition, as the diol component with naphthalene skeleton and/or fluorene skeleton, two [4-(2-hydroxyl-oxethyl) phenyl] fluorenes of 9,9-can be enumerated, two [4-(2-the hydroxyl-oxethyl)-3-aminomethyl phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-3, the 5-3,5-dimethylphenyls] fluorenes of 9,9-, two [4-(2-the hydroxyl-oxethyl)-3-ethylphenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-3, the 5-diethyl phenyl] fluorenes of 9,9-, two [4-(2-the hydroxyl-oxethyl)-3-propyl group phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-3, the 5-dipropyl phenyl] fluorenes of 9,9-, two [4-(2-the hydroxyl-oxethyl)-3-isopropyl phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-3, the 5-diisopropyl phenyls] fluorenes of 9,9-, two [4-(2-the hydroxyl-oxethyl)-3-n-butylphenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-3, the 5-di-n-butyl phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl) 10-3-isobutyl phenenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-3, the 5-diisobutyl phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-3-(1-methyl-propyl) phenyl] fluorenes of 9,9-, 9,9-two [two (1-methyl-propyl) phenyl of 4-(2-hydroxyl-oxethyl)-3,5-] fluorenes, two [4-(2-the hydroxyl-oxethyl)-3-phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-3, the 5-diphenyl phenyl] fluorenes of 9,9-, two [4-(2-the hydroxyl-oxethyl)-3-benzyl phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-3, the 5-dibenzylphenyl] fluorenes of 9,9-, two [4-(4-hydroxybutoxy) phenyl] fluorenes of two [4-(3-hydroxy propyloxy group) phenyl] fluorenes of 9,9-9,9-, Isosorbide-5-Nitrae-dihydroxy naphthlene, 2,6-dihydroxy naphthlene etc., but do not limit this.

As mentioned above must containing the monomer component with sulfonic acid composition in the mylar of stack membrane of the present invention (C layer), the preferred monomer component of carboxylic acid composition containing having more than 3 yuan further.For carboxylic acid composition, by making the polybasic carboxylic acid composition of more than 3 yuan carry out copolymerization, carboxyl can be imported at the side chain of mylar.As the monomer with sulfonic acid composition, can enumerate such as, the alkali metal salt, alkali earth metal salt etc. of sulfoisophthalic acid, 5-sulfoisophthalic acid, 4-sulfosalicylic phthalate, 4-sulfo group naphthalene-2,7-dioctyl phthalate, 5-[4-sulfophenoxy] M-phthalic acid.In addition, as the monomer of polybasic carboxylic acid composition with more than 3 yuan, except the polybasic carboxylic acids such as trimellitic acid, also acid anhydrides can be used.Specifically can enumerate, 1, 2, 4, 5-ethylene-dimalonic acid dianhydride (PMA), 1, 2, 3, 4-pentane tetracarboxylic acid dianhydride, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, 5-(2, 5-dioxotetrahydro furans)-3-methyl-3-cyclohexene-1, 2-dicarboxylic acid anhydride, 5-(2, 5-dioxotetrahydro furans)-3-cyclohexene-1, 2-dicarboxylic acid anhydride, cyclopentane tetracarboxylic acid dianhydride, 2, 3, 6, 7-naphthalenetetracarbacidic acidic dianhydride, 1, 2, 5, 6-naphthalenetetracarbacidic acidic dianhydride, ethylene glycol bis trimelitic dianhydride, 2, 2 ', 3, 3 '-bibenzene tetracarboxylic dianhydride, thiophene-2, 3, 4, 5-tetracarboxylic acid dianhydride, dimalonic acid dianhydride etc.And then, also by with this sulfonic group of neutralization such as ammonia and/or NaOH and/or carboxylic acid group, make sulphonate-base or carboxylate group.Alkali is become and hydrophily and water-soluble raising by making end.In addition, when the copolymerization of polybasic carboxylic acid composition, preferred use following methods: make the PEPA (polyester oligomer) that dicarboxylic acid component and diol component react and obtain, the polybasic acid anhydride with more than 3 yuan carries out reacting and imports carboxyl at the side chain of mylar.By using said method, more effectively carboxyl can be imported at the side chain of mylar, thus preferably.The monomer of the monomer of what these were above-mentioned have sulfonic acid composition and the polybasic carboxylic acid composition with more than 3 yuan can be organized at polyester (A) and jointly use in polyester (B) group.In addition, form the monomer component of above-mentioned mylar, coating layer (C layer) composition can be extracted by with an organic solvent waiting, passing through ¹h-NMR or ¹³c-NMR, IR, thermal decomposition GC/MS and combine these methods to analyze extract.

In stack membrane of the present invention (C layer), do not damage characteristic of the present invention scope can containing not belonging to polyester (A) group, the mylar (below as polyester (C) group) of arbitrary group (not meeting glass transition temperature (Tg) scope of any one) that polyester (B) is organized.As content when mylar entirety is 100 weight portion, be preferably below 30 weight portions, more preferably below 20 weight portions.When the content organized of polyester (C) is more than 30 weight portion, sometimes reduce with the cohesive of hard conating and/or durability.

In stack membrane of the present invention (C layer), as crosslinking agent contain melamine series crosslinking agent and/or azoles quinoline system crosslinking agent then, keeps excellent with the cohesive of hard conating, the bonding force particularly under wet-heat resisting environment, thus preferably.The content of melamine series crosslinking agent and/or azoles quinoline system crosslinking agent is preferably 20 ~ 80 weight portions relative to mylar 100 weight portion, more preferably 30 ~ 60 weight portions.When content is less than 20 weight portion, poor adhesion sometimes, during more than 80 weight portion, has the tendency that coating defects increases.Melamine series crosslinking agent of the present invention is not particularly limited, melamine, melamine and formaldehyde can be used to carry out condensation and the methylolated melamine derivative obtained, methylolated melamine and lower alcohol are reacted and partially or fully etherificate and the compound obtained and their mixture etc.Can be monomer as melamine series crosslinking agent, comprise any one of the condensation product of the polymer of more than dimer in addition, also can be their mixture.As the lower alcohol that etherificate uses, methyl alcohol, ethanol, isopropyl alcohol, n-butanol, isobutanol etc. can be used.By have in 1 molecule imino group, methylol or methoxy, butoxymethyl etc. alkoxy methyl as functional group, thus become imino-type methylated melamine resins, methylol type melmac, methylol type methylated melamine resins, completely alkyl type methylated melamine resins etc.Wherein most preferably methylolated melamine resin.And then, in order to promote the heat cure of melamine series crosslinking agent, such as, can use the acidic catalysts such as p-methyl benzenesulfonic acid.In addition, azoles quinoline system of the present invention crosslinking agent, as long as there is azoles quinoline base as functional group to be not particularly limited in this compound, preferably comprise: containing the monomer containing azoles quinoline base of more than at least a kind and other monomers of at least a kind are carried out copolymerization and obtain contain the copolymer of azoles quinoline base.

In stack membrane of the present invention (C layer), using the crosslinking agent except melamine series crosslinking agent and/or azoles quinoline system crosslinking agent in the scope not damaging characteristic of the present invention, can enumerate such as epoxy crosslinking agent, carbodiimide system crosslinking agent as preference.The kind of epoxy crosslinking agent is not particularly limited, can uses that such as D-sorbite polyglycidyl ether system, polyglycerol polyglycidyl ether (polyglycerol polyglycidyl ether) are, two glycerine polyglycidyl ether systems, polyethyleneglycol diglycidylether system and polyethyleneglycol diglycidylether system etc.In addition, as long as the compound having the carbodiimide of more than 1 or 2 or a cyanamide base of its tautomerism relation as functional group in molecule in carbodiimide system this compound of crosslinking agent is not particularly limited.As the concrete example of such carbodiimide compound, can enumerate dicyclohexyl methyl hydride carbodiimide, dicyclohexylcarbodiimide, tetramethyl xylylen carbodiimide, urea carbon modified diimine etc., these materials can use one kind or two or more mixture.

In stack membrane of the present invention (C layer), bonding (adhesion durability) with the initial bond widely of hard conating and wet-heat resisting to improve, preferably mixing acrylic resin.This is considered because, due to the difference of surface energy, there is rate of change with the polyester resin component as principal component in acrylic resin composition in stack membrane (C layer) on the thickness direction of stack membrane (C layer), becoming the superficial layer at hard conating interface, but the low acrylic resin composition more existence high with the cohesive of hard conating of hydrophily.Considering the formation in the stack membrane by taking as described so in addition, reducing with the reverberation at the interface of hard conating, and can prevent from interfering uneven deterioration.The formation of such stack membrane can observe its section to confirm with transmission-type microscope (TEM) after acrylic resin being carried out dyeing process.

Acrylic resin of the present invention, as the monomer component forming this acrylic resin, can use such as, alkyl acrylate, alkyl methacrylate (having methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, 2-ethylhexyl, lauryl, stearyl, cyclohexyl, phenyl, benzyl, phenylethyl etc. as alkyl); The hydroxyl monomers such as 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, 2-hydroxypropyl acrylate, methacrylic acid-2-hydroxy propyl ester; The amide-containing monomers such as acrylamide, Methacrylamide, N-methyl-propen acid amides, N-methyl-Methacrylamide, N-methylol-acrylamide, N-methylol-Methacrylamide, N, N-dihydroxymethyl-acrylamide, N-methoxy-acrylamide, N-methoxy-Methacrylamide, N-phenyl-acrylamide; The emulsion stabilities such as N, N-diethylamino ethyl-acrylate, N, N-diethylamino ethyl-methacrylate; Glycidyl acrylate, GMA etc. are containing epoxy based monomers; The monomer etc. containing carboxyl or its salt such as acrylic acid, methacrylic acid and their salt (lithium salts, sodium salt, sylvite etc.), these materials can use and one kind or two or morely carry out (be total to) and be polymerized.The glass transition temperature (Tg) of acrylic resin is not particularly limited, is preferably 0 ~ 90 DEG C, is more preferably 10 ~ 80 DEG C.During the acrylic resin using Tg low, there is the tendency that wet-heat resisting cohesive (adhesion durability) is deteriorated, when contrary Tg is too high, sometimes make film poor.In addition, this acrylic resin preferable particle size is aqueous dispersion and the emulsion of below 100nm, and then more preferably particle diameter is the aqueous dispersion of below 60nm.When acrylic resin is dissolved in water completely, sometimes poor with the wet-heat resisting cohesive (adhesion durability) of hard conating, in addition when particle diameter is greater than the emulsion of 100nm, the deteriorated appearance of film, is not suitable as hard coat film.The blending rate of acrylic resin, relative to mylar 100 weight portion, is preferably 5 ~ 30 weight portions, more preferably 10 ~ 30 weight portions.When the content of acrylic resin is less than 5 weight portion, the effect that improves of bonding force and/or wet-heat resisting cohesive (adhesion durability) is insufficient sometimes, time in addition more than 30 weight portion, has the tendency of interfering uneven deterioration.

In stack membrane of the present invention (C layer), in order to improve the uniformity of thickness and/or prevent the generation of coating defects, preferred interpolation surfactant, its content is preferably 0.5 ~ 3.0 weight portion relative to mylar 100 weight portion, more preferably 1.0 ~ 1.5 weight portions.When being less than 0.5 weight portion, the situation that the effect of surfactant is insufficient sometimes, time in addition more than 3.0 weight portion, finds and the tendency that the cohesive of hard conating worsens.The surfactant added in the present invention is not particularly limited, nonionic surfactant can be enumerated (such as, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, sorbitan fatty ester etc.), ionic surfactant (such as, the sulfuric ester of higher alcohol and salt thereof, alkylbenzenesulfonate, polyoxyethylene alkylphenyl sulfonate, alkyl (acid amides) betaine, alkyl dimethyl amine oxide etc.), fluorine system surfactant (such as fl muoroalkyl's salt, perfluoroalkyl benzene sulfonate, perfluoroalkyl quaternary ammonium salt salt, perfluoroalkyl polyoxy vinyl alcohol etc.), can by these materials a kind or two or more be used in combination.Wherein fluorine system surfactant is excellent in the uniformity and coating defects suppression of stack membrane (C layer), thus preferably.In addition, in order to improve levelability further, also with water-soluble solvent, can be able to enumerate such as, alcohols, the 1-METHYLPYRROLIDONE polar solvent such as methyl alcohol, ethanol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, butyl cellosolve, can use the one kind or two or more mixture of these materials.

In the present invention, by making containing particulate in stack membrane (C layer), easy slip and/or resistance to blocking improve, thus more preferably.Be not particularly limited as the particulate used, the inorganic particulate of cataloid, titanium oxide, aluminium oxide, zirconia, calcium carbonate, carbon black, zeolite particles etc. can be enumerated, and/or the organic filler such as acrylic particles, silicone particles, polyimide particle, " teflon (Teflon) " (registration mark) particle, cross-linked polyester particle, crosslinked polystyrene particle, cross-linking polymer particle, core-shell particles, can use these particles any one or also can and with multiple.The equal primary particle size of number of these particles is preferably in the scope of 10 ~ 600nm.So-called average primary particle diameter here in JIS-H7008 (2002), is defined through the growth of the single nuclei of crystallization and the particle diameter of the primary particle of the particle generated average.The average primary particle diameter of particle is more preferably in the scope of 20 ~ 500nm, preferred in the scope of 20 ~ 400nm further.Particle can use monodisperse particle in addition, also can use the agglutination particle of multiple particles aggregate.In addition, according to circumstances also can also with the multiple particle that average primary particle diameter is different.The addition of particle should according to the suitably adjusted design such as the thickness of stack membrane (C layer) and/or resin composition, average primary particle diameter, required easy slip and/or purposes, when stack membrane (C layer) entirety is 100 weight portion, preferably in the scope of 0.05 ~ 8 weight portion, more preferably in the scope of 0.1 ~ 5 weight portion.When average primary particle diameter is less than 10nm and/or when particle addition is less than 0.05 weight portion, sometimes easily slip and/or resistance to blocking insufficient, average primary particle diameter more than during 600nm and/or particle addition more than 8 weight portion time, have particle to come off and/or the tendency of deteriorated appearance.

And then in the stack membrane (C layer) of laminated polyester film of the present invention, various additives can be coordinated, such as the particulate, filler, antistatic agent, nucleator etc. of antioxidant, heat-resisting stabilizing agent, weatherability stabilizing agent, ultra-violet absorber, organically easy lubrication prescription, pigment, dyestuff, organic or inorganic in the scope not hindering effect of the present invention.

In addition, when implementing of the present invention, the coating process of coating layer is not particularly limited, can use such as, inverse painting method, spraying process, scraper rubbing method, gravure coating process, stick coating method, mould Tu Fa etc., if there is the membrane thickness unevenness of stack membrane (C layer), then easily generate interference after hard conating uneven.Therefore, in the present invention, the gravure coating process that the uneven uniformity of preferred thickness is high and scraper rubbing method, particularly preferably by utilizing the scraper coating method of metering scraper.

Form the polyester of substrate polyester film of the present invention (S layer), it is the high molecular general name of the main marriage chain using ester bond as main chain, as preferred polyester, can use to be selected from PETP, 2,6-polyethylene naphthalate, butylene terephthalate, α, the constituent of at least a kind of β-bis-(2-chlorophenoxy) ethane-4,4 '-dicarboxylate etc. is as the polyester of main composition composition.These constituents can only use a kind, and also two or more kinds may be used, if wherein synthetically judge quality, economy etc., then particularly preferably use the polyester using PETP as main composition composition.In addition, be used at hotwork, in the purposes of base material, also can using the poly-NDA second diester of heat resistance and/or excellent rigidity.In addition, these polyester, can further with part, be preferably other dicarboxylic acid component of less than 20 % by mole and/or diol component carries out copolymerization.

The limiting viscosity (according to JIS K7367 (2000), measuring in the o-chlorphenol of 25 DEG C) of above-mentioned polyester is preferably 0.4 ~ 1.2dl/g, is more preferably in the scope of 0.5 ~ 0.8dl/g.

And then, in this polyester, various additive can be added not make the degree of its characteristic degradation, such as, the particulate, filler, antistatic agent, nucleator, crosslinking agent etc. of antioxidant, heat-resisting stabilizing agent, weatherability stabilizing agent, ultra-violet absorber, organically easy lubrication prescription, pigment, dyestuff, organic or inorganic.Particularly preferably make in polyester film containing ultra-violet absorber to give ultraviolet partition ability.As ultra-violet absorber, preference example is as salicylic acid based compound, benzophenone based compound, BTA based compound, cyanoacrylate based compound and benzo piperazine ketone based compound, cyclic imide base ester based compound etc., the ultraviolet of 380nm cut off in property, tone etc. and M+P, M/P by polyester described later (M represents the concentration (mM %) of the catalyst metals element remained in film, P represents the concentration (mM %) of the P elements remained in film) the control aspect that improves dispersed effect performance degree set out, most preferably benzo piperazine ketone based compound.These compounds can a kind separately or two or more together and use.In addition can and with the stabilizing agent of HALS and/or antioxidant etc., particularly preferably and with the antioxidant of phosphorus system.

Here as the compound of BTA system, can illustrate such as, 2-(2H-BTA-2-base)-4, two (1-methyl isophthalic acid-phenylethyl) phenol of 6-, 2-(2H-BTA-2-base)-4-(1, 1, 3, 3-tetramethyl butyl) phenol, 2-(2H-BTA-2-base)-4-methylphenol, 2-(2H-BTA-2-base)-4, 6-bis--tert-butyl phenol, 2-(2H-BTA-2-base)-4, 6-di-tert-pentyl phenol, 2-(2H-BTA-2-base)-4-TBP, 2-(2 '-hydroxyl-3 '-the tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two-tert-butyl-phenyl)-5-chlorobenzotriazole etc.

As benzophenone based compound, can enumerate such as, 2-hydroxyl-4-octyloxybenzophenone, ESCALOL 567,2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,4-DihydroxyBenzophenone, BP-4 etc.

As benzo piperazine ketone based compound, can illustrate such as, 2-p-nitrophenyl-3,1-benzo piperazine-4-ketone, 2-(to benzoylphenyl)-3,1-benzo piperazine-4-ketone, 2-(2-naphthyl)-3,1-benzos piperazine-4-ketone, 2,2 '-TOPOT 2,2′ p phenylenebis (3,1-benzo piperazine-4-ketone), 2,2 '-(2,6-naphthylene) two (3,1-benzo piperazine-4-ketone) etc.

Laminated polyester film of the present invention, the transmissivity that the transmissivity of 380nm wavelength is preferably less than 5.0%, 380nm is more preferably less than 3.0%.This is being applicable to have in the display member purposes of display base protection; from the aspect of the UV protection function of other materials, other compounds; the transmissivity of the wavelength of regulation 380nm is in above-mentioned scope; by while the transmissivity of 380nm is controlled in this scope; control full light transmittance, mist degree, b value, thus can as the various display members such as LCD, Electronic Paper, EL display, plasma display, touch-screen component and/or the surface protection and/or the use of surperficial decorative film that are used in particular for mobile device.In addition, the interpolation of particulate reduces light transmittance and/or the such characteristic relating to the transparency of mist degree more, when thus adding, preferable particle size is as far as possible little, and the particulate with the particle diameter of about less than 1/4 of visible wavelength of scattering preferably not easily occurs, and its addition is also preferably trace.

Substrate polyester film of the present invention (S layer) is preferably double axial orientated polyester film.Here so-called " biaxial orientation ", the pattern by Wide angle X-ray diffraction display biaxial orientation is referred to.Double axial orientated polyester film can obtain usually as follows: the polyester sheet of unstretched state is stretched about 2.5 ~ 5.0 times respectively in leaf length direction and width, thereafter, heat-treats, complete crystalline orientation.

In addition, the substrate polyester film (S layer) used in the present invention can S layer self be the laminated structure of more than 2 layers.As laminated structure, can enumerate such as, have the complex film of internal layer portion and skin section, it is provided with the complex film that particle is not contained in fact in internal layer portion, skin section contains the layer of particle, and internal layer portion and skin section can be the polymer of chemically xenogenesis also can be polymer of the same race.In the display applications as main purpose of the present invention, in the optical characteristics of the transparency etc., not containing particle etc. in preferred S layer.The layer thickness of the S layer becoming base material is not particularly limited, suitably can selects according to purposes, be generally 10 ~ 500 μm, be preferably 20 ~ 300 μm, more preferably 38 ~ 250 μm.

Then using use as substrate polyester film (S layer) situation of PET (following, sometimes slightly PET) film be example so that the manufacture method of laminated polyester film of the present invention to be described, but to be not limited thereto.

After the PET particle of the limiting viscosity 0.5 ~ 0.8dl/g forming substrate polyester film (S layer) is carried out vacuum drying, be supplied in extruder, and dissolve at 260 ~ 300 DEG C, sheet is extruded into by T font nozzle, use electrostatic applying the tape casting to be wound in the minute surface curtain coating drum of surface temperature 10 ~ 60 DEG C, its cooling curing is made the PET film that do not stretch.This unstretching film is stretched 2.5 ~ 5.0 times in longitudinal direction (referring to that the direct of travel of film also claims " length direction ") between the roller being heated to 70 ~ 100 DEG C.Carry out Corona discharge Treatment in atmosphere as required to this film, make the wetting tension on this surface be more than 47mN/m, on its treated side, coating forms the water system paint of stack membrane (C layer).The laminated polyester film clip that this is applied holds and imports dry section, after making coating layer drying, heat the temperature of 70 ~ 150 DEG C, then 2.5 ~ 5.0 times are stretched the thermal treatment zone of 70 ~ 150 DEG C in transverse direction (referring to that the direction vertical with the direct of travel of film also claims " width ") continuously, then heat treatment in 5 ~ 40 seconds is carried out the thermal treatment zone of 200 ~ 240 DEG C, through the cooling zone of 100 ~ 200 DEG C, obtain at the substrate polyester film completing crystalline orientation (S layer) superimposed layer the polyester film of stack membrane (C layer).In addition, in above-mentioned heat treatment, the relaxation processes of 3 ~ 12% can be carried out as required.Biaxial stretch-formed can be longitudinal and transverse successively stretching or simultaneously biaxial stretch-formed any one, also after longitudinal and transverse stretching, can redraw in any one direction longitudinal and transverse in addition.The end of the Biaxially oriented, laminated polyester film obtained cut rear winding and makes intermediate, after using thereafter cutting cutter to be cut into the width of expectation, being wound in cylindric core, thus the polyester film roller of desired length can be obtained.In addition, embossed can be carried out to film both ends to improve volume appearance during winding.

Then the hard coat film being provided with hard conating on laminated polyester film of the present invention is described.

In the present invention, the material forming hard conating is not particularly limited, as long as the material of visible light transmissive line, the material that preferred light transmittance is high.As used material, be acrylic resin, polycarbonate-based resin, vinyl chloride-based resin, polyester based resin, polyurethane series resin, active ray gel-type resin etc.From the aspect such as marresistance, productivity ratio, particularly preferably use acrylic resin, polyurethane series resin, active ray gel-type resin.

As the active ray gel-type resin that the constituent of hard conating uses, as the monomer component forming this active ray gel-type resin, such as pentaerythrite three (methyl) acrylate can be used, pentaerythrite four (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two (methacryloylthiophenyl) sulfide, 2,4-dibromo phenyl (methyl) acrylate, 2,3,5-tribromo phenyl (methyl) acrylate, two (4-(methyl) acryloxy phenyl) propane of 2,2-, two (4-(methyl) acryloxy ethoxy phenyl) propane of 2,2-, two (4-(methyl) the acryloxy diethoxy phenyl) propane of 2,2-, two (4-(methyl) the acryloyl group five ethoxyl phenenyl) propane of 2,2-, two (4-(methyl) acryloyloxyethoxy-3, the 5-dibromo phenyl) propane of 2,2-, two (4-(methyl) acryloxy diethoxy-3, the 5-dibromo phenyl) propane of 2,2-, two (4-(methyl) acryloxy five ethyoxyl-3, the 5-dibromo phenyl) propane of 2,2-, two (4-(methyl) acryloyloxyethoxy-3, the 5-3,5-dimethylphenyl) propane of 2,2-, two (4-(methyl) acryloyloxyethoxy-3-phenyl) propane of 2,2-, two (4-(methyl) acryloxy phenyl) sulfone, two (4-(methyl) acryloxy ethoxy phenyl) sulfone, two (4-(methyl) acryloxy five ethoxyl phenenyl) sulfone, two (4-(methyl) acryloyloxyethoxy-3-phenyl) sulfone, two (4-(methyl) acryloyloxyethoxy-3,5-3,5-dimethylphenyl) sulfone, two (4-(methyl) acryloxy phenyl) sulfide, two (4-(methyl) acryloxy ethoxy phenyl) sulfide, two (4-(methyl) acryloxy five ethoxyl phenenyl) sulfide, two (4-(methyl) acryloyloxyethoxy-3-phenyl) sulfide, two (4-(methyl) acryloyloxyethoxy-3,5-3,5-dimethylphenyl) sulfide, two ((methyl) acryloyloxyethoxy) phosphate, multifunctional (methyl) acrylic compounds such as three ((methyl) acryloyloxyethoxy) phosphate, these materials can use one kind or two or more.

In addition, while these multifunctional (methyl) acrylic compounds, in order to control the hardness of active ray gel-type resin, the transparency, intensity, refractive index etc., styrene can be used, chlorostyrene, dichlorostyrene, bromstyrol, Dowspray 9, divinylbenzene, vinyltoluene, 1-vinyl naphthalene, 2-vinyl naphthalene, NVP, (methyl) phenyl acrylate, (methyl) benzyl acrylate, xenyl (methyl) acrylate, diallyl phthalate, dimethyl allyl ester, diallyl diphenyl ether, or barium, plumbous, antimony, titanium, tin, the metals such as zinc and (methyl) acrylic acid reactant etc.These materials can use one kind or two or more.

In addition, the record that " (methyl) acrylic compounds " is such is the record of simple expression " methacrylic acid based compound and acrylic compounds ", and the compound for other is stated too.

As the method making active ray gel-type resin solidify, such as, can use the method for irradiation ultraviolet radiation, now, preferably to the Photoepolymerizationinitiater initiater about above-claimed cpd interpolation 0.01 ~ 10 weight portion.

In the active ray gel-type resin used in the present invention, in order to improve operability, control coating film thickness during coating, in the scope not damaging effect of the present invention, the organic solvents such as isopropyl alcohol, ethyl acetate, MEK can be coordinated.

So-called active ray in the present invention, refer to that ultraviolet, electron ray, radioactive ray (alpha ray, β ray, gamma-rays etc.) etc. make the electromagnetic wave of the vinyl polymerization of acrylic acid series, in practicality, ultraviolet is easy, thus preferably.As ultraviolet source, ultraviolet fluorescent lamp, low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp, carbon arc lamp etc. can be used.In addition, although electron ray mode device is expensive and must operate under an inert gas, the aspect of Photoepolymerizationinitiater initiater, sensitising agent etc. is had to be favourable from can be free of.

In the present invention in order to protect hard conating self and laminated polyester film and/or component preferably to contain ultra-violet absorber from ultraviolet.As ultra-violet absorber, be not particularly limited, existing known ultra-violet absorber can be enumerated, such as salicylic acid based compound, cyanoacrylate based compound, benzophenone based compound, BTA based compound etc.Wherein, from viewpoints such as against weathers when using in outdoor etc., preferred benzophenone based compound and/or BTA based compound.As benzophenone based compound, ESCALOL 567 can be enumerated, 2, 4-dihydroxy benaophenonel, UV-531, 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone, 2, 2 '-dihydroxy-4, 4 '-dimethoxy-benzophenone, 2-hydroxyl-4-benzoyloxy benzophenone, 2, 2 '-dihydroxy-4-methoxy benzophenone, 2-hydroxyl-4-methoxyl group-5-sulfuryl benzophenone, 2, 2 ', 4, 4 '-tetrahydroxybenzophenone, 2, 2 '-dihydroxy-4, 4 '-dimethoxy-benzophenone, 2-hydroxyl-5-chlorobenzophenone, two-(2-methoxyl group-4-hydroxyl-5-benzoylphenyl) methane etc.In addition, as BTA based compound, 2-(2 '-hydroxy phenyl) BTA can be enumerated, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) BTA, 2-(2 '-hydroxy-5-methyl base phenyl)-5-butyl formate BTA, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-5,6-dichloro BTAs, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-5-ethyl sulfuryl BTA, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) BTA, 2-(2 '-hydroxyl-5 '-aminophenyl) BTA, 2-(2 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl) BTA, 2-(2 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl)-5-methoxyl group BTA, 2-(2 '-methyl-4 '-hydroxy phenyl) BTA, 2-(2 '-stearoyl-oxy-3 ', 5 '-3,5-dimethylphenyl)-5-methylbenzotrazole, 2-(2 '-hydroxy-5-methyl acid phenyl) BTA ethyl ester, and 2-(2 '-hydroxyl-3 '-methyl-5 '-tert-butyl-phenyl) BTA, 2-(2 '-hydroxyl-3 ', 5 '-two-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 '-the tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-5 '-methoxyphenyl) BTA, 2-(2 '-hydroxyl-3 ', 5 '-two-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-5 '-cyclohexyl phenyl) BTA, 2-(2 '-hydroxyl-4 ', 5 '-3,5-dimethylphenyl)-5-formic acid BTA butyl ester, 2-(2 '-hydroxyl-3 ', 5 '-dichlorophenyl) BTA, 2-(2 '-hydroxyl-4 ', 5 '-dichlorophenyl) BTA, 2-(2 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl)-5-ethyl sulfuryl BTA, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) BTA, 2-(2 '-hydroxyl-5 '-methoxyphenyl)-5-methylbenzotrazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-5-formic acid esters BTA, 2-(2 '-acetoxyl group-5 '-aminomethyl phenyl) BTA etc.

The content of the ultra-violet absorber in hard conating is preferably 0.5 weight portion ~ 30 weight portion, more preferably 3 ~ 20 weight portions in hard conating.When ultra-violet absorber is more than 30 weight portion, find the tendency that the case hardness reduction of hard conating and/or the bonding force of hard conating reduce.When being less than 0.5 weight portion in addition, ultraviolet radiation absorption function becomes insufficient sometimes.As the ultraviolet radiation absorption function of hard conating, by keeping the necessity of case hardness as above and/or bonding force, the light transmittance of usual wavelength 380nm is about 40 ~ 70%.Necessary ultraviolet radiation absorption amount is different according to using the purposes of this hard coat film different, during ultraviolet radiation absorption insufficiency of function, the light transmittance of 380nm can be made to be less than 1% by making substrate polyester rete contain ultra-violet absorber as described above.

The refractive index of hard conating of the present invention, adjusts with the form that the refringence at the interface with stack membrane (C layer) surface diminishes, thus the light of the reason becoming interference fringe can be suppressed to reflect.The refractive index of this hard conating is preferably 1.45 ~ 1.55, is more preferably 1.48 ~ 1.53.The thickness of hard conating should carry out suitable adjusted design according to use etc. in addition, is not particularly limited, and is generally 1 ~ 10 μm, is preferably 2 ~ 5 μm.If the thickness of hard conating is in this preferable range, then painting property fully shows firmly, on the other hand, also film will be caused curling due to contraction during hard coat layer.

In the present invention, preferably arrange on the surface of hard conating for suppressing the anti-reflection layer glimmered, and/or implement to be used for antipollution antifouling process.In addition, also can on hard conating successively lamination as the high index of refraction hard conating of anti-reflection layer and low-index layer, this is used as antireflection film.Anti-reflection layer is not particularly limited, can by utilizing the lamination of the coating of low-refraction compound and/or utilizing the lamination of the sputtering of the inorganic compound such as magnesium fluoride and/or silica and/or evaporation etc. to be formed.For antifouling process, the antifouling process utilizing siloxane-based resin, fluorine resin etc. can be implemented.

Embodiment

[determination method of physical property]

Below, formation of the present invention, effect is further illustrated by embodiment.In addition, the present invention is not limited to following embodiment.Before the description of each embodiment, record the assay method of various physical property.

(1) glass transition temperature (Tg) of mylar

The device that セ イ コ ー electronics industry (strain) SSC5200 processed デ ィ ス Network ス テ ー シ ョ Application is connected to セ イ コ ー electronics industry (strain) ロ ボ processed ッ ト DSC (differential scanning calorimeter) RDC220 and obtains by use measures.Sample (resin solid thing) 10mg is modulated on aluminium dish, after 5 minutes, carries out quenching process with liquid nitrogen at the heating temperatures of 300 DEG C.Thereafter measure while heating up with the speed of 20 DEG C/min, obtain DSC curve.Following methods is utilized to calculate glass transition temperature (Tg) by the DSC curve obtained.Near glass transition temperature (Tg), draw 2 extended lines along DSC curve, calculate glass transition temperature (Tg) (with reference to Fig. 1) by the intersection point of 1/2 straight line between extended line and DSC curve.

(2) spectral reflectance

After the length direction measuring the back side in the face black glossy band that 50mm is wide (large and (strain) ビ processed ニ ー ル テ ー プ NO.200-50-21: black) and meet in the mode of not mixing bubble sample and band is pasted, cut out the coupons that about 40mm is square, the light splitting specular reflectivity of incidence angle 5 ° is measured with spectrophotometer (Shimadzu Seisakusho Ltd.'s (strain) UV2450 processed uses specular reflectivity determination unit).Sample is positioned over the direction of analyzer, towards the front of analyzer and direction before and after making meets the length direction of sample.In addition in order to reflectivity is carried out standardization, use subsidiary Al2O3 plate as standard reflecting plate.Reflectivity measures in the scope of wavelength 400 ~ 700nm, using reflectivity be minimum wavelength as λ min (nm), will at the reflectivity of wavelength X min (nm) as Rmin (%).

(3) initial bond power is evaluated

(A) preparation of hard coat film

(a) hard coat film not containing ultra-violet absorber

The stack membrane (C layer) using metering bar coater the active ray gel-type resin (Japanese synthetic chemical industry (strain) purple light UV-1700B processed [refractive index: 1.50 ~ 1.51]) forming hard conating to be spread evenly across laminated polyester film makes the thickness after solidifying be 1.5 μm on the surface.Then, cumulative exposure intensity is made to be 300mJ/cm by light collecting type high-pressure sodium lamp (ア イ グ ラ Off ィ ッ Network ス (strain) H03-L31 processed) irradiation ultraviolet radiation with the exposure intensity of 120W/cm of the height being arranged at the surperficial 9cm of distance hard conating ², make it solidify, obtained at laminated polyester film superimposed layer the hard coat film of hard conating.In addition, in ultraviolet cumulative exposure strength detection, use industrial UV verifier (Japanese battery (strain) UVR-N1 processed).

(b) hard coat film containing ultra-violet absorber

The stack membrane (C layer) using metering bar coater the hard conating of the composition of following expression to be coated equably laminated polyester film make the thickness after solidifying be 1.5 μm.

Active ray gel-type resin (JSR (strain) オ プ processed ス タ ー Z7534) 100 weight portions

Ultra-violet absorber (ダ イ セ Le chemical industry (strain) プ ラ processed Network セ Le UVA103) 10 weight portions

Light trigger (BASF イ Le ガ キ ュ ア 1700) 5 weight portions

Then, after 100 DEG C of dryings, be that light collecting type high-pressure sodium lamp (ア イ グ ラ Off ィ ッ Network ス (strain) H03-L31 processed) irradiation ultraviolet radiation with the exposure intensity of 120W/cm of the height of 9cm makes cumulative exposure intensity be 600mJ/cm by being arranged at the surface of distance C layer ², make it solidify, obtained at laminated polyester film superimposed layer the hard coat film of hard conating.In addition, in ultraviolet cumulative exposure strength detection, use industrial UV verifier (Japanese battery (strain) UVR-N1 processed)

(B) initial bond

100 1mm are introduced at the hard conating of above-mentioned hard coat film ²cross-cut.Operation, except following, is carried out according to the order of 7 of JIS K5600-5-6 (1999).

Experimental condition and test number: the 7.1.1 item regardless of JIS K5600-5-6 (1999) specifies, experimental condition is 23 DEG C, relative humidity 65%.In addition, testing number is 1.

The maintenance of breadboard: the 7.1.2 item regardless of JIS K5600-5-6 (1999) specifies, curing condition is temperature 23 DEG C, relative humidity 65%, and curing time is 1 hour.

Cut number: the 7.1.3 item regardless of JIS K5600-5-6 (1999) specifies, cutting number is 11.

The interval of cutting: the 7.1.4 item regardless of JIS K5600-5-6 (1999) specifies, that cuts is spaced apart 1mm.

Utilize incision and the removing of the film of manually order: the regulation of the 7.2.5 item of inapplicable JISK5600-5-6 (1999).That is, brush brush is not used.In addition, the 7.2.6 item of JIS K5600-5-6 (1999) is only suitable for the regulation (" being positioned on grid by the direction of a group that the center of band is cut with the side of being parallel to as shown in Figure 3; with length more than 20mm minimum than the place of Box Section; make band smooth with finger ") of the 2nd paragraph, other regulation inapplicable.In addition, band uses cellophane band (ニ チ バ Application (strain) セ ロ processed テ ー プ (registration mark) CT405AP).

In addition, the stickup of band is carried out as follows: ((strain) オ ー デ ィ オ テ Network ニ カ HP515), back and forth presses 3 times with loading 19.6N/m, roller translational speed 5cm/ second to use hand roller.Then, the direction that band relative to hard coating surface direction is being 90 degree is peeled off with the speed of speed 10cm/ second second, carries out 4 Phase Evaluations by the remaining number being arranged at the grid of hard conating.In addition, when remaining number is 100/100 (remaining number/mensuration number), and then the ultraviolet cumulative exposure intensity of (A) item reduced by half again measure, be that the sample of 100/100 (remaining number/mensuration number) is evaluated as 5 by result.More than 5 is that initial bond is very good, and more than 4 is good, and 3 is realistic scale, and less than 2 is that initial bond is bad.

5:100/100 (remaining number/mensuration number): ultraviolet cumulative exposure intensity is reduced by half

4:100/100: ultraviolet irradiation intensity is ormal weight

More than 3:80/100, and lower than 100/100

More than 2:50/100, and lower than 80/100

1: lower than 50/100.

(4) wet-heat resisting cohesive

(A) high temperature and humidity test evaluation (wet-heat resisting bondability index)

The hard painting stack membrane not containing ultra-violet absorber and the hard painting stack membrane containing ultra-violet absorber is obtained by the method same with (3).The film obtained is placed 250 hours in the constant temperature and humidity cabinet of temperature 60 C, relative humidity 90%, obtains wet-heat resisting adhesive test sample.For the wet-heat resisting adhesive test sample obtained, carry out adhesion test by the method same with (3) (B), carry out 5 Phase Evaluations, as wet-heat resisting bondability index by the number of remaining grid.More than 5 is that wet-heat resisting cohesive is very good, and more than 4 is good, and 3 is realistic scale, and less than 2 is that wet-heat resisting cohesive is bad.

5:100/100 (remaining number/mensuration number)

More than 4:90/100, and lower than 100/100

More than 3:80/100, and lower than 90/100

More than 2:50/100, and lower than 80/100

1: lower than 50/100

(B) boiling test evaluation (boiling resistance bondability index)

The hard painting stack membrane not containing ultra-violet absorber and the hard painting stack membrane containing ultra-violet absorber is obtained by the method same with (3).The film obtained is placed 1 hour in the pure boiling water (100 DEG C) formed, obtains boiling resistance adhesive test sample.For the boiling resistance adhesive test sample obtained, carry out adhesion test by the method same with (3) (B), carry out 5 Phase Evaluations, as boiling resistance bondability index by the number of remaining grid.More than 5 is that boiling resistance cohesive is very good, and more than 4 is good, and 3,2 is realistic scale, and 1 is boiling resistance poor adhesion.In addition, boiling test is the evaluation under the more stringent condition of high temperature and humidity test, even if be evaluated as 1, as long as it is then realistic scale that the high temperature and humidity test of (4) (A) item is evaluated as more than 3.

5:100/100 (remaining number/mensuration number)

More than 4:90/100, and lower than 100/100

More than 3:80/100, and lower than 90/100

More than 2:50/100, and lower than 80/100

1: lower than less than 50/100

(5) interfere uneven

The hard coat film containing ultra-violet absorber is obtained by the method same with (3).Then, by the hard coat film obtained, cut out the sample of 8cm (laminated polyester film width) × 10cm (laminated polyester film length direction) size, black glossy band (ヤ マ ト (strain) ビ processed ニ ー ル テ ー プ NO.200-50-21: black) is pasted on the reverse side of hard conating with the form not taking in bubble.This sample is positioned over 30cm immediately below 3 wavelength fluorescent lamps (Matsushita Electric Industrial (strain) makes 3 wavelength shape whites in daytime (FL15EX-N15W)) in darkroom, by the degree of visualization interference fringe while changing visual angle, carry out following evaluation.The sample of realistic scale is the sample of B, more than A is good.In addition, the uneven method same with (1) (A) is interfered to sample from hard coat film.The judgement of result is implemented according to following benchmark, and more than B is acceptability limit.

S: interfere and unevenly substantially to cannot see

A: interfere and unevenly to see slightly

B: can see that weak interference is uneven.

C: interfere by force uneven.

(6) wetting tension on stack membrane (C layer) surface

Laminated polyester film is carried out maintenance in 24 hours under the condition of temperature 23 DEG C, relative humidity 65%.Thereafter, wetting tension is measured according to JIS K6768 (1999).

(7) TOF-SIMS of stack membrane (C layer) analyzes

Sulfonic group in stack membrane (C layer) and the analysis of carboxylic acid group, use time-of-flight type 2 secondary ion mass spectrum (TOF-SIMS) device to implement in following condition, use the 2 negative secondary ion peak intensities obtained to analyze stack membrane (C layer).

(device)

Device: TOF.SIMS5 (ION-TOF society system)

1 secondary ion: BI ₃ ⁺⁺, 1 secondary ion energy: 25KV

2 secondary ion polarity: negative

Back segment accelerates: 10KV

Measure vacuum: 4 × 10 ^-7pa

Pulse width: 9.0ns

Raster size: 300 μm of

Number of scans: 16scan

Pixel count: 256pixel

Mass range (m/z): 0 ~ 1500

(analytical method)

Be used as the CHO of 2 negative secondary ion kinds ₂ ^-(m/z45.00, derive from carboxylic acid group), SO ₃ ^-the peak intensity of the 2 negative secondary ion intensity entirety that the peak intensity removing of (m/z79.96, derive from sulfonic group) obtains, thus obtain standardized value (ratios relative to 2 negative secondary ion intensity entirety).

The preparation method of the resin used in each embodiment comparative example etc. is shown as a reference example.

The preparation of [reference example 1] mylar (A1)

2 are added as dicarboxylic acid component in a nitrogen atmosphere in transesterification reactor, 6-naphthalenedicarboxylic acid 88 molar part, 5-sulfoisophthalic acid sodium 6 molar part, ethylene glycol 100 molar part is added as diol component, butyl titanate (catalyst) 100 weight portion is added wherein relative to full dicarboxylic acid component 1,000,000 weight portion, after carrying out 5 hours esterifications at 160 ~ 240 DEG C, removing distillate.

Thereafter, further interpolation is as trimellitic acid 6 molar part of the polybasic carboxylic acid composition of more than 3 yuan and be the butyl titanate of 100 weight portions relative to full dicarboxylic acids 1,000,000 weight portion, 240 DEG C removing distillates until reactant become transparent till after, under the decompression of 220 ~ 280 DEG C, carry out polycondensation reaction, obtain mylar (A1).The Tg of this mylar is 120 DEG C.

Relative to above-mentioned mylar (A1) 100.0 weight portion add water 531.6 weight portion, 25 % by weight ammoniacal liquor 2.0 weight portion, butyl cellosolve 33.4 weight portion, 40 DEG C of dissolvings.Then this reaction vessel airtight, is warming up to 120 DEG C by the internal temperature of this container and carries out heating in 2 hours, obtaining the aqueous dispersion of mylar (A1).

The whole monomer of composition > of < mylar (A1) is 100 molar part.

(dicarboxylic acid component and polybasic carboxylic acid composition)

NDA 44 molar part

5-sulfoisophthalic acid sodium 3 molar part

1,3,5-trimellitic acid 3 molar part

(diol component)

Ethylene glycol 50 molar part

The preparation of [reference example 2] mylar (A2)

2 are added as dicarboxylic acid component in a nitrogen atmosphere in transesterification reactor, 6-naphthalene diformic acid dimethyl ester 80 molar part, 5-sulfoisophthalic acid sodium 10 molar part, 9 are added as diol component, 9-two [4-(2-hydroxyl-oxethyl) phenyl] fluorenes 80 molar part, ethylene glycol 20 molar part, adding wherein relative to dicarboxylate derivatives 1,000,000 weight portion is the butyl titanate (catalyst) of 100 weight portions, after carrying out 5 hours esterifications at 160 ~ 200 DEG C, distill out methyl alcohol.And then 240 DEG C, carry out reaction in 30 minutes under the decompression of 0.2MPa, obtain PEPA.

Then in PEPA, add 1,3,5-trimellitic acid 10 molar part as the polybasic carboxylic acid composition of more than 3 yuan, carry out reaction in 3 hours reaction temperature 160 ~ 180 DEG C, obtain mylar (A2).The Tg of this mylar is 135 DEG C.

Mix above-mentioned fluorenes copolymer polyester resin (A2) 100 weight portion and oxolane 400 weight portion, after dissolving at 80 DEG C, add water 500 weight portion of 80 DEG C, obtain the water/oxolane system solution of mylar (A2).Add butyl cellosolve 50 weight portion at the water obtained/oxolane system solution, and then distill the oxolane in the solution that obtains, add water after cooling, obtain the aqueous dispersion (10% concentration) of mylar (A2).

The whole monomer of composition > of < mylar (A2) is 100 molar part.

(dicarboxylic acid component and polybasic carboxylic acid composition)

NDA 40 molar part

5-sulfoisophthalic acid sodium 5 molar part

Trimellitic acid 5 molar part

(diol component)

Two [4-(2-hydroxyl-oxethyl) phenyl] fluorenes 40 molar part of 9,9-

Ethylene glycol 10 molar part

The preparation of [reference example 3] mylar (A3 ~ A5, B1 ~ B4, C1 ~ C2)

Except the composition being table 1 except preparing each composition, operating in the same manner as reference example 1 and preparing mylar and aqueous dispersion thereof.

The preparation of [reference example 4] acrylic resin

Under nitrogen atmosphere, under decompression state, in emulsion polymerization reactor, add neopelex 1 weight portion as emulsifying agent in 300 parts, the water becoming solvent, methyl methacrylate (MMA) 65 weight portion is added as monomer, ethyl acrylate (EMA) 30 weight portion, N hydroxymethyl acrylamide (N-MAM) 3 weight portion, acrylic acid (AA) 2 weight portion, 100 weight portion sodium peroxydisulfates (initator) are added wherein relative to whole monomer component 1,000,000 weight portion, after carrying out reaction in 10 hours at 30 ~ 80 DEG C, carrying out adjustment with ammonia spirit (alkali) makes pH value be 7.0 ~ 9.0.Thereafter, under the decompression of 70 DEG C, remove unreacted monomer, carry out concentrated obtaining acrylic emulsion 35%.The average grain diameter of acrylic emulsion is 45nm, Tg is 55 DEG C.

The composition > of < acrylic resin

Methyl methacrylate 65 weight portion

Ethyl acrylate 30 weight portion

N hydroxymethyl acrylamide 3 weight portion

Acrylic acid 2 weight portion.

The preparation of [reference example 5] PET particle (PET)

Terephthalic acid (TPA) is used as sour composition, spent glycol is made as diol component, in the polyester granulate obtained, add antimony trioxide (polymerization catalyst) makes antimony atoms be scaled 300ppm, carry out polycondensation reaction, obtain the PET particle (PET) of limiting viscosity 0.63dl/g, carboxyl terminal base unit weight 40 equivalents/ton.

[embodiment 1]

After carrying out drying in 4 hours at the PET particle obtained by the method for reference example 5 (limiting viscosity 0.63dl/g) in a vacuum 160 DEG C, be supplied in extruder and carry out dissolving extruding at 285 DEG C.After filtering with the filter carrying out stainless steel fibre sintering compression and the average mesh 5 μm that obtain, the filter that then obtains with average mesh 14 μm powder of stainless steel is sintered, be extruded into sheet by T font nozzle, the minute surface curtain coating using electrostatic applying the tape casting to be wound in surface temperature 20 DEG C is roused and carries out cooling curing.In addition, to be now arranged to the gap nozzle of the gap 2mm of 8 sections by length direction with the cold wind of wind speed 20m/s to film blowing temp 10 DEG C from the reverse side of curtain coating drum, to cool from two sides.

With preheat roll by after this unstretching film preheating, pharoid is used to be heated to while 90 DEG C, utilize the peripheral speed difference between roller to stretch 3.1 times at length direction from above-below direction, then be cooled to 25 DEG C with chill roll, make uniaxial orientation (uniaxial tension) film.Carry out Corona discharge Treatment in atmosphere to the two sides of this film, the surface tension of film is 55mN/m.

Then, in order to form stack membrane (C layer), metering bar coater is used following masking liquid to be coated the two sides of above-mentioned monadic stretching membrane.In addition, metal lean uses the line rod of diameter 13mm, wire diameter 0.1mm (#4).

< masking liquid >

Using mylar solid constituent as contain during 100 weight portion following composition, mylar solid constituent converted score is the aqueous solution of 5.0%.

Mylar (A1): 40 weight portions

Mylar (B1): 60 weight portions

Melamine series crosslinking agent (three and chemical society (strain) system " ニ カ ラ ッ Network " MW12LF): 40 weight portions (solid constituent conversion)

. azoles quinoline system crosslinking agent (Japanese catalyst (strain) system " エ Port Network ロ ス " WS500): 10 weight portions (solid constituent conversion)

The cataloid of particle diameter 140nm: 1.5 weight portions

Hold with clip the monadic stretching membrane being coated with stack membrane (C layer) and also carry out drying, preheating with atmosphere temperature 120 DEG C in an oven, then stretch 3.7 times at the drawing zone of 120 DEG C at width continuously.By biaxial orientation (biaxial stretch-formed) film that obtains after heat treatment in 10 seconds is carried out in the thermal treatment zone of 230 DEG C, carry out the relaxation processes of 5% while being undertaken cooling by 230 DEG C to 120 DEG C, be then cooled to 50 DEG C.Then reel after removing width both ends, obtained at substrate polyester film (S layer) superimposed layer the laminated polyester film of the thickness 188 μm of stack membrane (C layer), mist degree 0.9% (JIS K7105 (1981)).The characteristic of the laminated polyester film obtained is shown in table 3.And have the initial bond power of hard conating of UV-absorbing layer, durability, interference uneven (average fluctuation amplitude) any one all excellent, particularly initial bond power and interference uneven reduction solidification excellence, be applicable as hard conating film.In addition, the hard coat film laminated polyester film of the embodiment 1 obtained according to [assay method of physical property] (3) (A) (b) item being provided with the hard conating containing ultra-violet absorber is 50% in the transmissivity of wavelength 380nm.

[embodiment 2 ~ 26, comparative example 1 ~ 9]

Except the composition of stack membrane (C layer) is as except table 2, obtain laminated polyester film according to embodiment 1.The characteristic of the laminated polyester film obtained is shown in table 3.In addition, being coated with agent concentration in embodiment 19 is 4.6%, and being coated with agent concentration in embodiment 20 is 5.4%.In addition, for embodiment 21, as the raw material of substrate polyester film (S layer), use relative in embodiment 1 record polyethylene terephthalate resin contain 0.5 % by weight as 2 of ultra-violet absorber, 2 '-(Isosorbide-5-Nitrae-phenylene) two (4H-3,1-benzo piperazine-4-ketone) raw material.

(cohesive)

Stack membrane (C layer) is the mylar containing sulfonic acid composition, the wetting tension on stack membrane (C layer) surface in the scope of 35 ~ 45mN/m, with the wet-heat resisting bondability index of the hard conating containing ultra-violet absorber 3 ~ 5 acceptability limit.In addition, as by glass transition temperature (Tg) be 110 ~ 140 DEG C polyester (A) group and glass transition temperature (Tg) be 40 ~ 90 DEG C polyester (B) group with 10/90 ~ 60/40 ratio mix, and have in polyester (A) group and polyester (B) group containing sulfonic acid composition monomer and contain the monomer of polybasic carboxylic acid composition of more than 3 yuan when, initial bond and the further excellent result of wet-heat resisting cohesive (adhesion durability), the wet-heat resisting bondability index of this extraneous embodiment 24 ~ 26 is 3 be limited to practical threshold level.The ratio particularly organized at polyester (A) group and polyester (B) is 30/70 ~ 50/50, and the content (SA) of the contained monomer containing sulfonic acid composition is 3 ~ 5 molar part in polyester (A) group, content (CA) containing the monomer of the polybasic carboxylic acid compositions of more than 3 yuan is 3 ~ 8 molar part, and then the content (SB) of the contained monomer containing sulfonic acid composition is 3 ~ 5 molar part in polyester (B) group, content (CB) containing the monomer of the polybasic carboxylic acid compositions of more than 3 yuan is 3 ~ 8 molar part, melamine series and/or azoles quinoline system crosslinking agent are 30 ~ 60 weight portions, stack membrane (C layer) surface wetting tension meet the level of 36 ~ 43mN/m under, be called initial bond, the result that wet-heat resisting cohesive (adhesion durability) is excellent all especially.(embodiment 1,3,9,10,13-20,22,23)

Consider because in mylar, containing sulfonic acid composition, the hydrophily of resin increases, to the bonding force at initial stage, there is effect, when thinking that carboxylic acid composition and sulfonic acid composition compare in addition, the contribution improved initial bond power is little, but wet-heat resisting cohesive (adhesion durability) is excellent and comprise the hydrophilic effect guaranteeing resin, by containing aforesaid amount suitably, the balance of initial bond power and wet-heat resisting cohesive (adhesion durability) can be obtained, thus the cohesive that performance is excellent especially.For the standardized value of 2 secondary ion intensity deriving from sulfonic acid composition and carboxylic acid composition, SO ₃ ^-be 0.2 × 10 ^-2~ 2.0 × 10 ^-2, CHO ₂ ^-be 0.3 × 10 ^-2~ 1.5 × 10 ^-2scope become preferred result, the wet-heat resisting poor adhesion of this extraneous comparative example 1,2,5,6,7,9.

In addition, for 2 polyester groups that glass transition temperature (Tg) is different, consider that glass transition temperature (Tg) higher polyester (A) is even if the variation of group molecular structure under high temperature, high humidity is also less, therefore relation is had with adhesion durability, in addition, consider that the motility of the molecule that the polyester (B) that glass transition temperature (Tg) is lower is organized is high, consider with the bonding force relation at initial stage dark.

Comparative example 1 initial bond do not organized containing polyester (B) is poor, organizes wet-heat resisting poor adhesion in the comparative example 8 of the low polyester C1 of glass transition temperature (Tg) using than polyester (B).In addition, the embodiment 24 not containing sulfonic acid composition in polyester (B) group finds the tendency of initial bond difference, and poor embodiment 6 compares initial bond with embodiment 1 and reduces slightly.On the other hand, the comparative example 2,4 do not organized containing polyester (A), and the comparative example 3,6 in polyester containing more sulfonic acid composition, wetting tension being more than 45mN/m, result is the good but wet-heat resisting poor adhesion of initial bond.And then, for the embodiment 26 not containing sulfonic acid composition in polyester (A) group, the embodiment 25 not containing carboxylic acid composition, find the tendency that durability reduces.Consider this mainly because the initial bond between the performance fusible polyester of wet-heat resisting (A) composition organized and hard conating and humidity resistance are insufficient state, thus in preferred polyester (A) group containing sulfonic acid composition and carboxylic acid composition.

And then the result of the embodiment 13-16 containing 5 ~ 30 parts by weight of acrylic acid system resins in stack membrane (C layer) is that wet-heat resisting cohesive improves further.This is considered because, due to the difference of surface energy in the stack membrane (C layer) acrylic resin composition and there is rate of change as the polyester resin component of principal component on the thickness direction of stack membrane (C layer), becoming the superficial layer at hard conating interface, the more existence of acrylic resin composition that hydrophily is low but high with the cohesive of hard conating.Considering the formation by taking in stack membrane as above in addition, reducing with the reverberation at the interface of hard conating, also can prevent from interfering uneven deterioration.

(interfering uneven)

When the minimum λ min of the surface reflectivity of stack membrane (C layer) is 500 ~ 600nm, being acceptability limit, is result good especially during 530 ~ 570nm.Uneven deterioration is interfered until qualified limit level as in the embodiment 19,20 near the boundary of acceptability limit.In addition, be acceptability limit value 4.0 ~ 6.0% of the reflectivity Rmin of wavelength X min time, be good result 4.8 ~ 5.3% time.Interfere uneven difference in this extraneous comparative example 1 and for can not level, in addition close to the embodiment 4,5,14 of boundary, compare for qualified level with good scope but observe in comparative example 2,7 and interfere uneven deterioration.

(ultraviolet-absorbing)

In embodiment 21, by in substrate polyester film (S layer) containing ultra-violet absorber, according to (3) (A) (b) item obtain on the laminated polyester film of embodiment 21, the hard conating containing ultra-violet absorber is set and the hard coat film that obtain is be less than 0.1% so extremely low value in the transmissivity of wavelength 380nm.The hard coat film obtained be form the hard conating of this film, laminated polyester film layer and the component protected by this hard coat film any one to all excellent hard coat film of ultraviolet durability.

[table 2-2]

[table 2-4]

Industry utilizability

Laminated polyester film of the present invention, hard conating shows extensively and the bonding force of excellent in te pins of durability with to have with UV absorption function etc. be the various functions of representative, and then can show when hard conating is set and interfere uneven repressed good appearance characteristic, be thus useful as hard conating film.Particularly with the bonding force excellent in te pins of durability of hard conating with UV absorption function, use in preferably used in a mobile device surface protection and/or antireflection film, touch-screen film, surperficial decorative film etc.

Symbol description

1 DSC curve

2 extended lines

3 1/2 straight lines

4 glass transition temperatures (Tg)

The reflectance curve of 5 stack membranes (C layer) side

The minimum of 6 reflectivity

Claims (9)

1. a laminated polyester film, it is characterized in that, take mylar as the stack membrane of principal component and the laminated polyester film of C layer at least one lamination of substrate polyester film and S layer, the wetting tension on stack membrane and C layer surface is 35 ~ 45mN/m, and mylar contained in stack membrane and C layer meets following (a) ~ (c):

(a) in stack membrane and C layer containing glass transition temperature Tg to be the polyester A group of 110 ~ 140 DEG C and glass transition temperature Tg the be polyester B group of 40 ~ 90 DEG C,

(b) at least polyester A group and polyester B group any one in, containing there is the monomer of sulfonic acid composition and there is the monomer of polybasic carboxylic acid composition of more than 3 yuan,

C the blending ratio of () polyester A group and polyester B group counts 10/90 ~ 60/40 with weight rate,

Mylar contained in stack membrane and C layer, containing glass transition temperature Tg to be the polyester A group of 110 ~ 140 DEG C and glass transition temperature Tg the be polyester B group of 40 ~ 90 DEG C, and polyester A group and polyester B group are containing having the monomer of sulfonic acid composition and having the monomer of polybasic carboxylic acid composition of more than 3 yuan, and then, whole monomer components 100 molar part contained in relative to polyester A group, the containing ratio with the monomer of sulfonic acid composition in this monomer component is SA, the containing ratio with the monomer of the polybasic carboxylic acid composition of more than 3 yuan is CA, and relative to whole monomer components 100 molar part contained in polyester B group, the containing ratio with the monomer of sulfonic acid composition in this monomer component is SB, when the containing ratio with the monomer of the polybasic carboxylic acid composition of more than 3 yuan is CB, meet with following formula (d) ~ (g),

1≤SA≤10 ... formula (d)

1≤SB≤10 ... formula (e)

1≤CA≤10 ... formula (f)

1≤CB≤10 ... formula (g),

The unit of described SA, SB, CA and CB is molar part.

2. a laminated polyester film, it is characterized in that, take mylar as the stack membrane of principal component and the laminated polyester film of C layer at least one lamination of substrate polyester film and S layer, form in the mylar of this stack membrane and C layer containing the monomer with sulfonic acid composition, and the wetting tension on stack membrane and C layer surface is 35 ~ 45mN/m, for analyzing stack membrane and the surperficial following 2 secondary ion peak kind obtained of C layer with time-of-flight type 2 secondary ion mass spectrum and TOF-SIMS, the standardized value of intensity is in following ranges

CHO ₂ ^-be 0.3 × 10 ^-2~ 1.5 × 10 ^-2,

SO ₃ ^-be 0.2 × 10 ^-2~ 2.0 × 10 ^-2.

3. laminated polyester film according to claim 1 and 2, in stack membrane and C layer containing melamine series and/or azoles quinoline system crosslinking agent, the content of this crosslinking agent is relative to mylar content 100 weight portion, containing 20 ~ 80 weight portions.

4. laminated polyester film according to claim 1 and 2, contain acrylic resin in stack membrane and C layer, the content of this acrylic resin is relative to mylar content 100 weight portion, containing 5 ~ 30 weight portions.

5. laminated polyester film according to claim 1 and 2, the spectral reflectance curve of stack membrane and C layer side surface exists at wavelength 500 ~ 600nm becomes minimum wavelength X min, is 4.0 ~ 6.0% at the reflectivity Rmin of λ min.

6. a hard coat film, it is the stack membrane of laminated polyester film described in any one of Claims 1 to 5 and C layer superimposed layer hard conating.

7. the manufacture method of a laminated polyester film, it has following operation: mylar melting is shaped to the operation of sheet, carries out biaxial stretch-formed operation at length direction and width and at least in the side face side of film, stack membrane is carried out the operation of lamination, and this operation of stack membrane being carried out lamination comprises by being coated with at least side of substrate polyester film and S layer the operation that following resin combination carrys out laminated resin layer

Described resin combination is the resin combination at least containing glass transition temperature Tg to be the polyester A group of 110 ~ 140 DEG C and glass transition temperature Tg the be polyester B group of 40 ~ 90 DEG C, in polyester A group and polyester B group at least in any one, containing there is the monomer of sulfonic acid composition and there is the monomer of polybasic carboxylic acid composition of more than 3 yuan, and the weight rate of polyester A group and polyester B group is 10/90 ~ 60/40

Described resin combination meets following necessary condition:

Whole monomer components 100 molar part contained in relative to polyester A group, the containing ratio with sulfonic monomer in this monomer component is SA, the containing ratio with the monomer of the polybasic carboxylic acid base of more than 3 yuan is CA, and relative to whole monomer components 100 molar part contained in polyester B group, the containing ratio with sulfonic monomer in this monomer component is SB, when the containing ratio with the monomer of the polybasic carboxylic acid base of more than 3 yuan is CB, meet with following formula (d) ~ (g)

1≤SA≤10 ... formula (d)

1≤SB≤10 ... formula (e)

1≤CA≤10 ... formula (f)

1≤CB≤10 ... formula (g),

The unit of described SA, SB, CA and CB is molar part.

8. the manufacture method of laminated polyester film according to claim 7, described resin combination meets following necessary condition:

Resin combination further containing melamine series and/or azoles quinoline based compound, the content of this compound, relative to mylar content 100 weight portion, is 20 ~ 80 weight portions.

9. the manufacture method of the laminated polyester film according to claim 7 or 8, described resin combination meets following necessary condition:

Resin combination is further containing acrylic resin, and the content of this acrylic resin, relative to mylar content 100 weight portion, is 5 ~ 30 weight portions.